Hydrolysis resistant organomodified silylated ionic surfactants

ABSTRACT

The present invention provides for a composition comprising a silane having the formula:
 
(R 1 )(R 2 )(R 3 )Si—R 4 —Si(R 5 )(R 6 )(R 7 )
 
wherein
         R 1 , R 2 , R 3 , R 5 , and R 6  are each independently selected from the group consisting of 1 to 6 monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 7 to 10 carbons containing an aryl group;   R 4  is a hydrocarbon group of 1 to 3 carbons;   R 7  comprises an anionic, cationic or zwitterionic substituent. The silanes of the present invention exhibit resistance to hydrolysis over a wide pH range.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional patent applicationSer. No. 60/869,432 filed Dec. 11, 2006.

FIELD OF THE INVENTION

The present invention relates to silane compositions that exhibitresistance to hydrolysis over a wide pH range. More particularly thepresent invention relates to such hydrolysis-resistant silanes having aresistance to hydrolysis between a pH of about 2 to a pH of about 12.

BACKGROUND OF THE INVENTION

The topical application of liquid compositions to the surfaces of bothanimate and inanimate objects to effect a desired change involve theprocesses of controlling wetting, spreading, foaming, detergency, andthe like. When used in aqueous solutions to improve the delivery ofactive ingredients to the surface being treated, trisiloxane-typecompounds have been found to be useful in enabling the control of theseprocesses to achieve the desired effect. However, the trisiloxanecompounds may only be used in a narrow pH range, ranging from a slightlyacidic pH of 6 to a very mildly basic pH of 7.5. Outside this narrow pHrange, the trisiloxane compounds are not stable to hydrolysis,undergoing rapid decomposition.

SUMMARY OF THE INVENTION

The present invention provides for an silane compound or compositionsthereof useful as a surfactant having the general formula:(R¹)(R²)(R³)Si—R⁴—Si(R⁵)(R⁶)(R⁷)wherein

R¹, R², R³, R⁵, and R⁶ are each independently selected from the groupconsisting of 1 to 6 monovalent hydrocarbon radicals, aryl, and ahydrocarbon group of 7 to 10 carbons containing an aryl group;

R⁴ is a hydrocarbon group of 1 to 3 carbons.

R⁷ is R⁸- R^(A), R⁹- R^(C), and R¹⁰- R^(Z);

R⁸ is selected from the group consisting of R¹¹(O)_(t)(R¹²)_(u)(O)_(v)—,

where R¹¹ and R¹² are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R¹³ isa divalent hydrocarbon group of 2 to 4 carbon atoms; R¹⁴ is a divalenthydrocarbon group of 1 to 6 carbons, that may each be optionallybranched; subscripts t, u and v are zero or 1. The subscripts a, b and care zero or positive and satisfy the following relationships:1≦a+b+c≦10 with a≧1.

R^(A) is a monovalent radical selected from the group consisting of—SO₃M^(K), —C(═O)CH₂CH(R¹⁵)COO-M^(K); —PO₃HM^(K); —COOM^(K); where R¹⁵is H or —SO₃M^(K); M^(K) is a cation selected from the group consistingof Na⁺, K⁺, Ca²⁺, NH₄ ⁺, Li⁺, and monovalent ammonium ions derived frommono-, di- and trialkylamines of 2 to 4 carbons or mono-, di- andtrialkanolamines of 2 to 4 carbons.

R⁹ is a monovalent radical selected from the group consisting of

R¹⁶(O)_(w)(R¹⁷)_(x)— andR¹⁸O(C₂H₄O)_(d)(C₃H₆O)_(e)(C₄H₈O)_(f)CH₂CH(OH)CH₂—;

where R¹⁶ and R¹⁷ are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R¹⁸ isa divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts w and xare zero or 1. The subscripts d, e and f are zero or positive andsatisfy the following relationships:1≦d+e+f≦10 with d≧1.

R^(C) is selected from N(R¹⁹)(R²⁰),

where R¹⁹ and R²⁰ are independently selected from the group consistingof H, a branched or linear monovalent hydrocarbon radical of 1 to 4carbons, R²⁶N(R²⁹)(R³⁰), and —R²⁷O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R²⁸.The subscripts g, h and are zero or positive and satisfy the followingrelationships:1≦g+h+i≦10 with g≧1.

R²¹, R²³, R²⁴, R²⁵ are each independently selected from the groupsconsisting of H, a branched or linear monovalent hydrocarbon radical of1 to 4 carbons.

R²² is a monovalent radical selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, or—R³¹O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³²; the subscripts j, k and l arezero or positive and satisfy the following relationships:1≦j+k+1≦10 with j≧1.

R²⁶ is a divalent hydrocarbon radical of 1 to 6 carbons, optionallysubstituted with a heterocyclic group containing nitrogen, sulfur,oxygen or combinations thereof orR³³O(C₂H₄O)_(m)(C₃H₆O)_(n)(C₄H₈O)_(o)R³⁴; the subscripts m, n and o arezero or positive and satisfy the following relationships:1≦m+n+o≦10 with m≧1.

R²⁹ and R³⁰ are independently selected from the group consisting of H ora branched or linear monovalent hydrocarbon radical of 1 to 4 carbons.

R²⁷, R³¹ and R³³ are independently selected from the group consisting ofa divalent hydrocarbon group of 2 to 4 carbon atoms.

R²⁸ is a monovalent radical selected from the group consisting of H, amonovalent hydrocarbon radical of 1 to 6 carbons and N(R⁴⁰)(R⁴¹).

R³² and R³⁴ are independently selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, andR³⁷N(R³⁸)(R³⁹); where R³⁷ is a divalent hydrocarbon radical of 1 to 6carbons. R³⁵, R³⁶, R³⁸ and R³⁹ are independently selected from the groupconsisting of H and branched or linear monovalent hydrocarbon radicalsof 1 to 4 carbons.

R¹⁰ is a monovalent radical selected from the group consisting ofR⁴⁰(O)_(y)(R⁴¹)_(z)— andR⁴²O(C₂H₄O)_(p)(C₃H₆O)_(q)(C₄H₈O)_(r)CH₂CH(OH)CH₂—; where R⁴⁰ and R⁴¹are each independently selected from the group consisting of a divalenthydrocarbon group of 1 to 4 carbon atoms, that may each be optionallysubstituted with one or more OH radicals; R⁴² is a divalent hydrocarbongroup of 2 to 4 carbon atoms; subscripts y and z are zero or 1. Thesubscripts p, q and r are zero or positive and satisfy the followingrelationships:1≦p+q+r≦10 with p ≧1.R^(Z) is —N—(R⁴³)(R⁴⁴)_(α)R⁴⁵SO₃(M^(K))_(β),—N—(R⁴⁶)(R⁴⁷)_(γ)R⁴⁸COO(M^(K))_(δ), —N⁺—(R⁴⁹)(R⁵⁰)R⁵¹OP(═O)(A)(B) or,(—C(═O)N(R⁵²)R⁵³N—(R⁵⁴)(R⁵⁵))⁺—(R⁵⁶OP(═O)(A)(B))(X⁻)_(ε);where R⁴³, R⁴⁴, R⁴⁶, R⁴⁷, R⁴⁹, R⁵⁰, R⁵², R⁵⁴ and R⁵⁵ are independentlyselected from the group consisting of H, a branched or linear monovalenthydrocarbon radical of 1 to 4 carbons, and an alkanolamine group of 2 to4 carbons. R⁴⁵ is a divalent group of 3 to 4 carbons; subscripts α, β, γand δ are zero or 1 subject to the following relationships: α+β isselected from the group consisting of 1 and γ+6 is selected from thegroup consisting of 1.

R⁴⁸ and R⁵¹ are independently a divalent group of 1 to 4 carbons.

R⁵³ and R⁵⁶ are each independently a divalent group of 2 to 4 carbons.

A and B are selected from O⁻ and OM^(K); X is an anion selected from thegroup of anions consisting of Cl, Br, and I; the subscript ε is 0, 1 or2.

Particularly useful embodiments of the present invention are exemplifiedby the following choices for species: R¹, R², R³, R⁵ and R⁶ are methyl;R⁴ is —CH₂CH₂— or —CH₂CH₂CH₂—; R¹¹ is —CH₂CH₂CH₂—; R¹² is—CH₂CH(OH)CH₂—; R¹³ is —CH₂CH₂—; R¹⁴ is —CH₂CH₂CH₂—, —CH(CH₃)CH₂CH₂—, or—CH₂CH(CH₃)CH₂—; a, b and c=0; t=1, u=1, v=0; R¹⁵═H; M^(K) is Na⁺, K⁺ orNH₄ ⁺; R¹⁶ is —CH₂CH₂CH₂—; R¹⁷ is —CH₂CH(OH)CH₂—; R¹⁸ is —CH₂CH₂CH₂—; d,e, and f=0; w=1, x=1; R¹⁹ and R²⁰ are H, methyl, ethyl, propyl,isopropyl or —R²⁷O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R²⁸; R²⁷ is—CH₂CH₂CH₂—; g is 1-5, h and i=0; R²⁷ is H or methyl; R²¹ and R²³ are H;R²²═H, methyl or —R³¹O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³²; R³¹ is—CH₂CH₂CH₂—; j is 1-5, k and I=0; R³² is H or methyl; R²⁴ and R²⁵ are H;R⁴⁰ is —CH₂CH₂CH₂—; R⁴¹ is —CH₂CH(CH₃)CH₂—;

y and z=1; R⁴² is —CH₂CH₂CH₂—; p is 1-5, q and r=0; R⁴³ and R⁴⁴ are H ormethyl; R⁴⁵ is —CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂—; M^(K)=Na⁺, K⁺ or NH₄ ⁺;

R⁴⁶ and R⁴⁷ are H or methyl; R⁴⁸ is —CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂—;

R⁴⁹ and R⁵⁰ are H or methyl; and R⁵², R⁵⁴ and R⁵⁵ are H or methyl.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, integer values of stoichiometric subscripts refer tomolecular species and non-integer values of stoichiometric subscriptsrefer to a mixture of molecular species on a molecular weight averagebasis, a number average basis or a mole fraction basis.

The present invention provides for an silane compound or compositionsthereof useful as a surfactant having the general formula:(R¹)(R²)(R³)S¹—R⁴—Si(R⁵)(R⁶)(R⁷)wherein

R¹, R², R³, R⁵, and R⁶ are each independently selected from the groupconsisting of 1 to 6 monovalent hydrocarbon radicals, aryl, and ahydrocarbon group of 7 to 10 carbons containing an aryl group;

R⁴ is a hydrocarbon group of 1 to 3 carbons.

R⁷ is R⁸- R^(A), R⁹- R^(C), and R¹⁰- R^(Z);

R⁸ is selected from the group consisting of R¹¹(O)_(t)(R¹²)_(u)(O)_(v)—,

where R¹¹ and R¹² are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R¹³ isa divalent hydrocarbon group of 2 to 4 carbon atoms; R¹⁴ is a divalenthydrocarbon group of 1 to 6 carbons, that may each be optionallybranched; subscripts t, u and v are zero or 1. The subscripts a, b and care zero or positive and satisfy the following relationships:1≦a+b+c≦10 with a≧1.

R^(A) is a monovalent radical selected from the group consisting of—SO₃M^(K),

—C(═O)CH₂CH(R¹⁵)COO⁻M^(K); —PO₃HM^(K); —COOM^(K); where R¹⁵ is H or—SO₃M^(K); M^(K) is a cation selected from the group consisting of Na⁺,K⁺, Ca²⁺, NH₄ ⁺, Li⁺, and monovalent ammonium ions derived from mono-,di- and trialkylamines of 2 to 4 carbons or mono-, di- andtrialkanolamines of 2 to 4 carbons.

R⁹ is a monovalent radical selected from the group consisting of

R¹⁶(O)_(w)(R¹⁷)_(x)— andR¹⁸O(C₂H₄O)_(d)(C₃H₆O)_(e)(C₄H₈O)_(f)CH₂CH(OH)CH₂—;

where R¹⁶ and R¹⁷ are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R¹⁸ isa divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts w and xare zero or 1. The subscripts d, e and f are zero or positive andsatisfy the following relationships:1≦d+e+f≦10 with d≧1.

R^(C) is selected from N(R¹⁹)(R²⁰),

where R¹⁹ and R²⁰ are independently selected from the group consistingof H, a branched or linear monovalent hydrocarbon radical of 1 to 4carbons, R²⁶N(R²⁹)(R³⁰), and —R²⁷O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R²⁸.The subscripts g, h and are zero or positive and satisfy the followingrelationships:1≦g+h+i≦10 with g≧1.

R²¹, R²³, R²⁴, R²⁵ are each independently selected from the groupsconsisting of H, a branched or linear monovalent hydrocarbon radical of1 to 4 carbons.

R²² is a monovalent radical selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, or—R³¹O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³²; the subscripts j, k and l arezero or positive and satisfy the following relationships:1≦j+k+1≦10 with j≧1.

R²⁶ is a divalent hydrocarbon radical of 1 to 6 carbons, optionallysubstituted with a heterocyclic group containing nitrogen, sulfur,oxygen or combinations thereof orR³³O(C₂H₄O)_(m)(C₃H₆O)_(n)(C₄H₈O)_(o)R³⁴; the subscripts m, n and o arezero or positive and satisfy the following relationships:1≦m+n+o≦10 with m≧1.

R²⁹ and R³⁰ are independently selected from the group consisting of H ora branched or linear monovalent hydrocarbon radical of 1 to 4 carbons.

R²⁷, R³¹ and R³³ are independently selected from the group consisting ofa divalent hydrocarbon group of 2 to 4 carbon atoms.

R²⁸ is a monovalent radical selected from the group consisting of H, amonovalent hydrocarbon radical of 1 to 6 carbons and N(R⁴⁰)(R⁴¹).

R³² and R³⁴ are independently selected from the group consisting of H, abranched or linear monovalent hydrocarbon radical of 1 to 4 carbons, andR³⁷N(R³⁸)(R³⁹); where R³⁷ is a divalent hydrocarbon radical of 1 to 6carbons. R³⁵, R³⁶, R³⁸ and R³⁹ are independently selected from the groupconsisting of H and branched or linear monovalent hydrocarbon radicalsof 1 to 4 carbons.

R¹⁰ is a monovalent radical selected from the group consisting of

R⁴⁰(O)_(y) (R⁴¹)_(z)— andR⁴²O(C₂H₄O)_(p)(C₃H₆O)_(q)(C₄H₈O)_(r)CH₂CH(OH)CH₂—;

where R⁴⁰ and R⁴¹ are each independently selected from the groupconsisting of a divalent hydrocarbon group of 1 to 4 carbon atoms, thatmay each be optionally substituted with one or more OH radicals; R⁴² isa divalent hydrocarbon group of 2 to 4 carbon atoms; subscripts y and zare zero or 1. The subscripts p, q and r are zero or positive andsatisfy the following relationships:1≦p+q+r≦10 with p≧1.R^(Z) is —N—(R⁴³)(R⁴⁴)_(α)R⁴⁵SO₃(M^(K))_(β),—N—(R⁴⁶)(R⁴⁷)_(γ)R⁴⁸COO(M^(K))_(δ), —N⁺—(R⁴⁹)(R⁵⁰)R⁵¹OP(═O)(A)(B) or,(—C(═O)N(R⁵²)R⁵³N—(R⁵⁴)(R⁵⁵))⁺—(R⁵⁶OP(═O)(A)(B))(X⁻)_(ε);where R⁴³, R⁴⁴, R⁴⁶, R⁴⁷, R⁴⁹, R⁵⁰, R⁵², R⁵⁴ and R⁵⁵ are independentlyselected from the group consisting of H, a branched or linear monovalenthydrocarbon radical of 1 to 4 carbons, and an alkanolamine group of 2 to4 carbons. R⁴⁵ is a divalent group of 3 to 4 carbons; subscripts α, β, γand δ are zero or 1 subject to the following relationships: α+β isselected from the group consisting of 1 and γ+δ is selected from thegroup consisting of 1.

R⁴³ and R⁵⁶ are independently a divalent group of 1 to 4 carbons.

R⁵³ and R⁵⁶ are each independently a divalent group of 2 to 4 carbons.

A and B are selected from O⁻ and OM^(K); X is an anion selected from thegroup of anions consisting of Cl, Br, and I; the subscript is 0, 1 or 2.

Particularly useful embodiments of the present invention are exemplifiedby the following choices for species: R¹, R², R³, R⁵ and R⁶ are methyl;R⁴ is —CH₂CH₂— or —CH₂CH₂CH₂—; R¹¹ is —CH₂CH₂CH₂—; R¹² is—CH₂CH(OH)CH₂—; R¹³ is —CH₂CH₂—; R¹⁴ is —CH₂CH₂CH₂—, —CH(CH₃)CH₂CH₂—, or—CH₂CH(CH₃)CH₂—; a, b and c=0; t=1, u=1, v=0; R¹⁵═H; MK is Na⁺, K⁺ orNH₄ ⁺; R¹⁶ is —CH₂CH₂CH₂—; R¹⁷ is —CH₂CH(OH)CH₂—; R¹⁸ is —CH₂CH₂CH₂—; d,e, and f=0; w=1, x=1; R¹⁹ and R²⁰ are H, methyl, ethyl, propyl,isopropyl or —R²⁷O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R²⁸; R²⁷ is—CH₂CH₂CH₂—; g is 1-5, h and i=0; R²⁷ is H or methyl; R²¹ and R²³ are H;R²²═H, methyl or —R³¹O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³²; R³¹ is—CH₂CH₂CH₂—; j is 1-5, k and l=0; R³² is H or methyl; R²⁴ and R²⁵ are H;R⁴⁰ is —CH₂CH₂CH₂—; R⁴¹ is —CH₂CH(CH₃)CH₂—;

y and z=1; R⁴² is —CH₂CH₂CH₂—; p is 1-5, q and r=0; R⁴³ and R⁴⁴ are H ormethyl; R⁴⁵ is —CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂—; M^(K)═Na⁺, K⁺ or NH₄ ⁺;

R⁴⁶ and R⁴⁷ are H or methyl; R⁴⁸ is —CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂—;

R⁴⁹ and R⁵⁰ are H or methyl; and R⁵², R⁵⁴ and R⁵⁵ are H or methyl.

One method of producing the composition of the present invention is toreact a molecule of the following formula:(R¹)(R²)(R³)Si—R⁴—Si(R⁵)(R⁶)(R′)where R′ is H, wherein the definitions and relationships are laterdefined and consistent with those defined above, under hydrosilylationconditions, with an olefinically modified epoxy-containing moiety, suchas allyl glycidyl ether or vinyl cyclohexene oxide, which areincorporated here as examples, and not set forth to limit other possibleolefinically modified epoxy components, followed by subsequent reactionwith an amine-containing group.

Epoxy-modified carbosilanes are straightforwardly prepared through theuse of a hydrosilylation reaction to graft the olefinically modified(i.e. vinyl, allyl or methallyl) epoxy group onto the hydride (SiH)intermediate of the carbosilane of the present invention.

Precious metal catalysts suitable for making epoxy-substituted silanesare also well known in the art and comprise complexes of rhodium,ruthenium, palladium, osmium, iridium, and/or platinum. Many types ofplatinum catalysts for this SiH-olefin addition reaction are known andsuch platinum catalysts may be used to generate the compositions of thepresent invention. The platinum compound can be selected from thosehaving the formula (PtC₂Olefin) and H(PtCl₃Olefin) as described in U.S.Pat. No. 3,159,601, hereby incorporated by reference. A further platinumcontaining material can be a complex of chloroplatinic acid with up to 2moles per gram of platinum of a member selected from the classconsisting of alcohols, ethers, aldehydes and mixtures thereof asdescribed in U.S. Pat. No. 3,220,972, hereby incorporated by reference.Yet another group of platinum containing materials useful in thispresent invention is described in U.S. Pat. Nos. 3,715,334; 3,775,452and 3,814,730 (Karstedt). Additional background concerning the art maybe found in J. L. Spier, “Homogeneous Catalysis of Hydrosilation byTransition Metals”, in Advances in Organometallic Chemistry, volume 17,pages 407 through 447, F. G. A. Stone and R. West editors, published byAcademic Press (New York, 1979). Those skilled in the art can easilydetermine an effective amount of platinum catalyst. Generally aneffective amount ranges from about 0.1 to 50 parts per million of thetotal silane composition.

Uses for the Compositions of the Present Invention:

A. Pesticide—Agriculture, Horticulture, Turf, Ornamental and Forestry

Many pesticide applications require the addition of an adjuvant to thespray mixture to provide wetting and spreading on foliar surfaces. Oftenthat adjuvant is a surfactant, which can perform a variety of functions,such as increasing spray droplet retention on difficult to wet leafsurfaces, enhance spreading to improve spray coverage, or to providepenetration of the herbicide into the plant cuticle. These adjuvants areprovided either as a tank-side additive or used as a component inpesticide formulations.

Typical uses for pesticides include agricultural, horticultural, turf,ornamental, home and garden, veterinary and forestry applications.

The pesticidal compositions of the present invention also include atleast one pesticide, where the silane of the present invention ispresent at an amount sufficient to deliver between 0.005% and 2% to thefinal use concentration, either as a concentrate or diluted in a tankmix. Optionally the pesticidal composition may include excipients,cosurfactants, solvents, foam control agents, deposition aids, driftretardants, biologicals, micronutrients, fertilizers and the like. Theterm pesticide means any compound used to destroy pests, e.g.,rodenticides, insecticides, miticides, fungicides, and herbicides.Illustrative examples of pesticides that can be employed include, butare not limited to, growth regulators, photosynthesis inhibitors,pigment inhibitors, mitotic disrupters, lipid biosynthesis inhibitors,cell wall inhibitors, and cell membrane disrupters. The amount ofpesticide employed in compositions of the invention varies with the typeof pesticide employed. More specific examples of pesticide compoundsthat can be used with the compositions of the invention are, but notlimited to, herbicides and growth regulators, such as phenoxy aceticacids, phenoxy propionic acids, phenoxy butyric acids, benzoic acids,triazines and s-triazines, substituted ureas, uracils, bentazon,desmedipham, methazole, phenmedipham, pyridate, amitrole, clomazone,fluridone, norflurazone, dinitroanilines, isopropalin, oryzalin,pendimethalin, prodiamine, trifluralin, glyphosate, sulfonylureas,imidazolinones, clethodim, diclofop-methyl, fenoxaprop-ethyl,fluazifop-p-butyl, haloxyfop-methyl, quizalofop, sethoxydim,dichlobenil, isoxaben, and bipyridylium compounds.

Fungicide compositions that can be used with the present inventioninclude, but are not limited to, aldimorph, tridemorph, dodemorph,dimethomorph; flusilazol, azaconazole, cyproconazole, epoxiconazole,furconazole, propiconazole, tebuconazole and the like; imazalil,thiophanate, benomyl carbendazim, chlorothialonil, dicloran,trifloxystrobin, fluoxystrobin, dimoxystrobin, azoxystrobin, furcaranil,prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicin,dodine, and metalaxyl.

Insecticide, larvacide, miticide and ovacide compounds that can be usedwith the composition of the present invention, but not limited to,Bacillus thuringiensis, spinosad, abamectin, doramectin, lepimectin,pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boricacid, chlordimeform, novaluron, bistrifluoron, triflumuron,diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kelevan,dimethoate, azinphos-ethyl, azinphos-methyl, izoxathion, chlorpyrifos,clofentezine, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrinand the like.

The pesticide may be a liquid or a solid. If a solid, it is preferablethat it is soluble in a solvent, or the silane of the present invention,prior to application, and the silane may act as a solvent, or surfactantfor such solubility or additional surfactants may perform this function.

Agricultural Excipients:

Buffers, preservatives and other standard excipients known in the artalso may be included in the composition.

Solvents may also be included in compositions of the present invention.These solvents are in a liquid state at room temperature. Examplesinclude water, alcohols, aromatic solvents, oils (i.e. mineral oil,vegetable oil, silicone oil, and so forth), lower alkyl esters ofvegetable oils, fatty acids, ketones, glycols, polyethylene glycols,diols, paraffinics, and so forth. Particular solvents would be2,2,4-trimethyl, 1-3-pentane diol and alkoxylated (especiallyethoxylated) versions thereof as illustrated in U.S. Pat. No. 5,674,832herein incorporated by reference, or N-methyl-pyrrilidone.

Cosurfactants:

Moreover, other cosurfactants, which have short chain hydrophobes thatdo not interfere with superspreading as described in U.S. Pat. No.5,558,806 are herein included by reference.

The cosurfactants useful herein include nonionic, cationic, anionic,amphoteric, zwitterionic, polymeric surfactants, or any mixture thereof.

Surfactants are typically hydrocarbon based, silicone based orfluorocarbon based.

Useful surfactants include alkoxylates, especially ethoxylates,containing block copolymers including copolymers of ethylene oxide,propylene oxide, butylene oxide, and mixtures thereof;alkylarylalkoxylates, especially ethoxylates or propoxylates and theirderivatives including alkyl phenol ethoxylate; arylarylalkoxylates,especially ethoxylates or propoxylates, and their derivatives; aminealkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fattyalcohol alkoxylates; alkyl sulfonates; alkyl benzene and alkylnaphthalene sulfonates; sulfated fatty alcohols, amines or acid amides;acid esters of sodium isethionate; esters of sodium sulfosuccinate;sulfated or sulfonated fatty acid esters; petroleum sulfonates; N-acylsarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and soforth.

Specific examples include alkyl acetylenic diols (SURFONYL-AirProducts), pyrrilodone based surfactants (e.g., SURFADONE-LP 100-ISP),2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates (e.g., RHODASURF DA530-Rhodia), ethylene diamine alkoxylates (TETRONICS-BASF), and ethyleneoxide/propylene oxide copolymers (PLURONICS-BASF) and Gemini typesurfactants (Rhodia).

Preferred surfactants include ethylene oxide/propylene oxide copolymers(EO/PO); amine ethoxylates; alkyl polyglycosides; oxo-tridecyl alcoholethoxylates, and so forth.

In a preferred embodiment, the agrochemical composition of the presentinvention further comprises one or more agrochemical ingredients.Suitable agrochemical ingredients include, but not limited to,herbicides, insecticides, growth regulators, fungicides, miticides,acaricides, fertilizers, biologicals, plant nutritionals,micronutrients, biocides, paraffinic mineral oil, methylated seed oils(i.e. methylsoyate or methylcanolate), vegetable oils (such as soybeanoil and canola oil), water conditioning agents such as Choice® (LovelandIndustries, Greeley, Colo.) and Quest (Helena Chemical, Collierville,Tenn.), modified clays such as Surround® (Englehard Corp.,), foamcontrol agents, surfactants, wetting agents, dispersants, emulsifiers,deposition aids, antidrift components, and water.

Suitable agrochemical compositions are made by combining, in a mannerknown in the art, such as by mixing, one or more of the above componentswith the silane of the present invention, either as a tank-mix, or as an“in-can” formulation. The term “tank-mix” means the addition of at leastone agrochemical to a spray medium, such as water or oil, at the pointof use. The term “in-can” refers to a formulation or concentratecontaining at least one agrochemical component. The “in-can” formulationmay then diluted to use concentration at the point of use, typically ina tank-mix, or it may be used undiluted.

The silane compositions of the present invention may be utilized inagricultural emulsions. The different types of emulsions are explainedhereinafter as varieties of personal care compositions.

B. Coatings

Typically, coatings formulations will require a wetting agent orsurfactant for the purpose of emulsification, compatibilization ofcomponents, leveling, flow and reduction of surface defects.Additionally, these additives may provide improvements in the cured ordry film, such as improved abrasion resistance, antiblocking,hydrophilic and hydrophobic properties. Coating formulations may existas solvent-borne coatings, water-borne coatings and powder coatings.

The coatings components may be employed as architecture coatings, OEMproduct coatings such as automotive coatings and coil coatings, specialpurpose coatings such as industrial maintenance coatings and marinecoatings. Typical synthetic resin types for coatings substrates includepolyesters, polyurethanes, polycarbonates, acrylics and epoxies.

C. Personal Care

In a preferred embodiment, the silane of the present inventioncomprises, per 100 parts by weight (“pbw”) of the personal carecomposition, from 0.1 to 99 pbw, more preferably from 0.5 pbw to 30 pbwand still more preferably from 1 to 15 pbw of the silane and from 1 pbwto 99.9 pbw, more preferably from 70 pbw to 99.5 pbw, and still morepreferably from 85 pbw to 99 pbw of the personal care composition.

The silane compositions of the present invention may be utilized inpersonal care emulsions, such as lotions, and creams. As is generallyknown, emulsions comprise at least two immiscible phases, one of whichis continuous and the other discontinuous. Further, emulsions may beliquids with varying viscosities or solids. Additionally the particlesize of the emulsions may render them microemulsions, and when theparticle sizes are sufficiently small, microemulsions may betransparent. Further, it is also possible to prepare emulsions ofemulsions and these are generally known as multiple emulsions. Theseemulsions may be:

1) aqueous emulsions where the discontinuous phase comprises water andthe continuous phase comprises the silane of the present invention;

2) aqueous emulsions where the discontinuous phase comprises the silaneof the present invention and the continuous phase comprises water;

3) non-aqueous emulsions where the discontinuous phase comprises anon-aqueous hydroxylic solvent and the continuous phase comprises thesilane of the present invention; and

4) non-aqueous emulsions where the discontinuous phase comprises thesilane of the present invention and the continuous phase comprises anon-aqueous hydroxylic organic solvent.

Non-aqueous emulsions comprising a silicone phase are described in U.S.Pat. Nos. 6,060,546 and 6,271,295, the disclosures of which are herewithand hereby specifically incorporated by reference.

As used herein, the term “non-aqueous hydroxylic organic compound” meanshydroxyl-containing organic compounds exemplified by alcohols, glycols,polyhydric alcohols and polymeric glycols, and mixtures thereof that areliquid at room temperature, e.g. about 25° C., and about one atmospherepressure. The non-aqueous organic hydroxylic solvents are selected fromthe group consisting of hydroxyl-containing organic compounds comprisingalcohols, glycols, polyhydric alcohols and polymeric glycols, andmixtures thereof that are liquid at room temperature, e.g. about 25° C.,and about one atmosphere pressure. Preferably the non-aqueous hydroxylicorganic solvent is selected from the group consisting of ethyleneglycol, ethanol, propyl alcohol, iso-propyl alcohol, propylene glycol,dipropylene glycol, tripropylene glycol, butylene glycol, iso-butyleneglycol, methyl propane diol, glycerin, sorbitol, polyethylene glycol,polypropylene glycol mono alkyl ethers, polyoxyalkylene copolymers andmixtures thereof.

Once the desired form is attained whether as a silicone only phase, ananhydrous mixture comprising the silicone phase, a hydrous mixturecomprising the silicone phase, a water-in-oil emulsion, an oil-in-wateremulsion, or either of the two non-aqueous emulsions or variationsthereon, the resulting material is usually a cream or lotion withimproved deposition properties and good feel characteristics. It iscapable of being blended into formulations for hair care, skin care,antiperspirants, sunscreens, cosmetics, color cosmetics, insectrepellants, vitamin and hormone carriers, fragrance carriers and thelike.

The personal care applications where the silane of the present inventionand the silicone compositions derived therefrom of the present inventionmay be employed include, but are not limited to, deodorants,antiperspirants, antiperspirant/deodorants, shaving products, skinlotions, moisturizers, toners, bath products, cleansing products, haircare products such as shampoos, conditioners, mousses, styling gels,hair sprays, hair dyes, hair color products, hair bleaches, wavingproducts, hair straighteners, manicure products such as nail polish,nail polish remover, nails creams and lotions, cuticle softeners,protective creams such as sunscreen, insect repellent and anti-agingproducts, color cosmetics such as lipsticks, foundations, face powders,eye liners, eye shadows, blushes, makeup, mascaras and other personalcare formulations where silicone components have been conventionallyadded, as well as drug delivery systems for topical application ofmedicinal compositions that are to be applied to the skin.

In a preferred embodiment, the personal care composition of the presentinvention further comprises one or more personal care ingredients.

Suitable personal care ingredients include, for example, emollients,moisturizers, humectants, pigments, including pearlescent pigments suchas, for example, bismuth oxychloride and titanium dioxide coated mica,colorants, fragrances, biocides, preservatives, antioxidants,anti-microbial agents, anti-fungal agents, antiperspirant agents,exfoliants, hormones, enzymes, medicinal compounds, vitamins, salts,electrolytes, alcohols, polyols, absorbing agents for ultravioletradiation, botanical extracts, surfactants, silicone oils, organic oils,waxes, film formers, thickening agents such as, for example, fumedsilica or hydrated silica, particulate fillers, such as for example,talc, kaolin, starch, modified starch, mica, nylon, clays, such as, forexample, bentonite and organo-modified clays.

Suitable personal care compositions are made by combining, in a mannerknown in the art, such as, for example, by mixing, one or more of theabove components with the silane. Suitable personal care compositionsmay be in the form of a single phase or in the form of an emulsion,including oil-in-water, water-in-oil and anhydrous emulsions where thesilicone phase may be either the discontinuous phase or the continuousphase, as well as multiple emulsions, such as, for example, oil-inwater-in-oil emulsions and water-in-oil-in water-emulsions.

In one useful embodiment, an antiperspirant composition comprises thesilane of the present invention and one or more active antiperspirantagents. Suitable antiperspirant agents include, for example, theCategory I active antiperspirant ingredients listed in the U.S. Food andDrug Administration's Oct. 10, 1993 Monograph on antiperspirant drugproducts for over-the-counter human use, such as, for example, aluminumhalides, aluminum hydroxyhalides, for example, aluminum chlorohydrate,and complexes or mixtures thereof with zirconyl oxyhalides and zirconylhydroxyhalides, such as for example, aluminum-zirconium chlorohydrate,aluminum zirconium glycine complexes, such as, for example, aluminumzirconium tetrachlorohydrex gly.

In another useful embodiment, a skin care composition comprises thesilane, and a vehicle, such as, for example, a silicone oil or anorganic oil. The skin care composition may, optionally, further includeemollients, such as, for example, triglyceride esters, wax esters, alkylor alkenyl esters of fatty acids or polyhydric alcohol esters and one ormore the known components conventionally used in skin care compositions,such as, for example, pigments, vitamins, such as, for example, VitaminA, Vitamin C and Vitamin E, sunscreen or sunblock compounds, such as,for example, titanium dioxide, zinc oxide, oxybenzone, octylmethoxycinnamate, butylmethoxy dibenzoylm ethane, p-aminobenzoic acid and octyldimethyl-p-aminobenzoic acid.

In another useful embodiment, a color cosmetic composition, such as, forexample, a lipstick, a makeup or a mascara composition comprises thesilane, and a coloring agent, such as a pigment, a water soluble dye ora liposoluble dye.

In another useful embodiment, the compositions of the present inventionare utilized in conjunction with fragrant materials. These fragrantmaterials may be fragrant compounds, encapsulated fragrant compounds, orfragrance releasing compounds that either the neat compounds or areencapsulated. Particularly compatible with the compositions of thepresent invention are the fragrance-releasing silicon-containingcompounds as disclosed in U.S. Pat. Nos. 6,046,156; 6,054,547;6,075,111; 6,077,923; 6,083,901; and 6,153,578; all of which are hereinand herewith specifically incorporated by reference.

The uses of the compositions of the present invention are not restrictedto personal care compositions, other products such as waxes, polishesand textiles treated with the compositions of the present invention arealso contemplated.

D. Home Care

Compositions of the present silane invention are useful in home careapplications, including laundry detergent and fabric softener,dishwashing liquids, wood and furniture polish, floor polish, tub andtile cleaners, toilet bowl cleaners, hard surface cleaners, windowcleaners, antifog agents, drain cleaners, auto-dishwashing detergentsand sheeting agents, carpet cleaners, prewash spotters, rust cleanersand scale removers.

E. Oil and Gas

Compositions of the present silane invention are useful in oil and gasapplications, including demulsification.

F. Water Treatment

Compositions comprising silane invention are useful for applicationsinvolving commercial and industrial open recirculating cooling watertowers, closed cooling water systems, cooling water conduits, heatexchangers, condensers, once-through cooling systems, Pasteurizers, airwashers, heat exchange systems, airconditioning/humidifiers/dehumidifiers, hydrostatic cookers, safetyand/or fire water protection storage systems, water scrubbers, disposalwells, influent water systems, including filtration and clarifiers,wastewater treatment, wastewater treatment tanks, conduits, filtrationbeds, digesters, clarifiers, holding ponds, settling lagoons, canals,odor control, ion exchange resin beds, membrane filtration, reverseosmosis, micro- and ultra-filtration, assisting in the removal ofbiofilms in cooling tower applications, heat exchangers and processwater systems, and the like.

G. Pulp and Paper

Compositions of the present silane invention are useful in pulp andpaper applications, such as paperboard defoamers, and wetting agents forthe pulping process.

The compositions of the present invention exhibit an enhanced resistanceto hydrolysis outside a pH range ranging from 6 to 7.5. Enhancedresistance to hydrolysis can be demonstrated by a variety of tests butas used herein enhanced resistance to hydrolysis means 50 mole percentor more of the hydrolysis-resistant composition of the present inventionremains unchanged or unreacted after a period of a twenty-four exposureto aqueous acidic conditions where the solution has a pH lower than 6 orafter a period of a twenty-four hour exposure to aqueous basicconditions where the solution has a pH greater than 7.5. Under acidicconditions the compositions of the present invention show a survival of50 mole percent of the original concentration or greater at a pH of 5 orless for a period of time in excess of 48 hours; specifically thecompositions of the present invention show a survival of 50 mole percentor greater at a pH of 5 or less for a period of time in excess of 2weeks; more specifically the compositions of the present invention showa survival of 50 mole percent or greater at a pH of 5 or less for aperiod of time in excess of 1 month; and most specifically thecompositions of the present invention show a survival of 50 mole percentor greater at a pH of 5 or less for a period of time in excess of 6months. Under basic conditions the compositions of the present inventionshow a survival of 50 mole percent or greater at a pH of 8 or more for aperiod of time in excess of 2 weeks; specifically the compositions ofthe present invention show a survival of 50 mole percent or greater at apH of 8 or more for a period of time in excess of 4 weeks; morespecifically the compositions of the present invention show a survivalof 50 mole percent or greater at a pH of 8 or more for a period of timein excess of 6 months; and most specifically the compositions of thepresent invention show a survival of 50 mole percent or greater at a pHof 8 or more for a period of time in excess of 1 year.

EXPERIMENTAL

The hydride intermediates for the silane compositions of the presentinvention, as well as comparative compositions were prepared asdescribed in the following examples.

Preparation Example 1

N,N-dimethyl aminopropyl pentamethyl carbodisilane (Figure 1). 16.0 gpentamethyl carbodisilane and 20 μL platinum1,3-divinyl-1,1,3,3-tetramethyldiloxane complex (0.3 wt % solution inxylene) were charged into 100 mL Schlenk flask. The mixture was heatedto 90° C. and 9.35 g N,N-dimethyl allyl amine was added dropwise in 20min. After addition, the reaction temperature was maintained at 90° C.for 3 hrs and the reaction was monitored by ¹HNMR. After removingsolvent under vacuum, the mixture was distilled under reduced pressure,and 17.0 g colorless oil was collected at 109-111° C./15 mmHg.

-   Figure 1. Reaction Sequence for Preparation of Amino Silane    Intermediate 1.

Preparation Example 2

3-({3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyl}-dimethyl-amino)-propane-1-sulfonate(Figure 2). 2.0 g N,N-dimethyl aminopropyl pentamethyl carbodisilane 1and 1.10 g1,3-propanesultone were dissolved in 15 ml dry THF. Themixture was heated to reflux overnight. After removing solvent, 3.03 gwhite solid was obtained.

-   Figure 2. Reaction Sequence for Preparation of Silane 2.

Preparation Example 3

4-([3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyl]-dimethyl-amino)-butane-1-sulfonate(Figure 3). 2.45 g N,N-dimethyl aminopropyl pentamethyl carbodisilane 1and 1.40 g1,4-butanesultone were dissolved in 10 ml dry THF. The mixturewas heated to reflux overnight. After removing solvent, 2.94 g whitesolid was obtained.

-   Figure 3. Reaction Sequence for Preparation of Silane 3.

Preparation Example 4

3-([3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyl]-dimethyl-amino)-acetate(Figure 4). 2.45 g N,N-dimethyl aminopropyl pentamethyl carbodisilane 1and 1.61 g sodium 2-bromoacetate were dissolved in 20 ml absoluteethanol. The suspension was heated to reflux overnight until all sodium2-bromoacetate disappeared. After removing the solvent, the residue waswashed with hexane and filtered 4.0 g white solid was obtained.

-   Figure 4. Reaction Sequence for Preparation of Silane 4.

Preparation Example 5

3-([3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyl]-dimethyl-amino)-ethanol(Figure 5). 2.45 g N,N-dimethyl aminopropyl pentamethyl carbodisilane 1and 1.37 g 2-bromoethanol were dissolved in 15 ml absolute ethanol. Themixture was heated to reflux for 16 hrs. After removing solvent, theresidue was vacuumed at 100 degree C./0.1 mmHg for 2 hrs. 3.33 g whitesolid was obtained.

-   Figure 5. Reaction Sequence for Preparation of Silane 5.

Preparation Example 6

3-([3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyl]-dimethyl-amino-ethoxy)-ethanol(Figure 6). 2.45 g N,N-dimethyl aminopropyl pentamethyl carbodisilane 1and 1.37 g 2-chloroethoxy ethanol were dissolved in 10 ml absoluteethanol. The mixture was heated to reflux for 20 hrs. After removingsolvent, the residue was vacuumed at 100 degree C./0.1 mmHg for 2 hrs.2.58 g light yellow solid was obtained.

-   Figure 6. Reaction Sequence for Preparation of Silane 6 (n=2).

Preparation Example 7

3-([3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyl]-dimethyl-amino-ethoxy-ethoxy)-ethanol(Figure 7). 1.96 g N,N-dimethyl aminopropyl pentamethyl carbodisilane 1and 1.26 g 2-(2-chloroethoxy)ethoxyethanol were dissolved in 10 mlabsolute ethanol. The mixture was heated to reflux for 20 hrs. Afterremoving solvent, the residue was vacuumed at 100 degree C./0.1 mmHg for2 hrs. 1.38 g light yellow solid was obtained.

-   Figure 7. Reaction Sequence for Preparation of Silane 7 (n=3).

Preparation Example 8

2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane(Figure 8). Pentamethyl dicarbodisilane (12.8 g; 80 mMol) andWilkinson's catalyst (30 ppm) were charged to a 100 mL RB 3 neck flaskequipped with a magnetic stirrer, reflux condenser, and N₂ inlet. Themixture was stirred and heated to 90° C. 2-Allyloxymethyl-oxirane (10 g;87.6 mMol) was placed in an addition funnel and added dropwise to theflask. The mixture was stirred and maintained at 90° C. for anadditional 4 hours. The reaction progress was followed by NMR. Excess2-allyloxymethyl-oxirane was removed by vacuum distillation.

-   Figure 8. Reaction Sequence for Preparation of Silylated Surfactant    Intermediate 8.

Preparation Example 9

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-propan-2-ol(Figure 9). 2-piperazin-1-yl-ethanol (0.95 g; 7.28 mMol) and 20 mL ofethanol were charged to a 100 ml RB flask equipped with a magneticstirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) was placed in an addition funnel and added dropwiseto the flask.

The mixture was stirred and maintained at 70° C. for additional 4 hours.After the reaction was complete, ethanol was stripped off on therotovap. The mixture was distilled under vacuum.

-   Figure 9. Reaction Sequence for Preparation of Silane 9.

Preparation Example 10

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-[2-(2-hydroxy-ethoxy)-ethylamino]-propan-2-ol(Figure 10). 2-(2-amino-ethoxy)-ethanol (3.83 g; 36.4 mMol) and 40 mL ofethanol were charged to a 100 mL RB flask equipped with a magneticstirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities and excess raw material.

-   Figure 10. Reaction Sequence for Preparation of Silane 10.

Preparation Example 11

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-[2-(2-hydroxy-ethoxy-ethoxy)-ethylamino]-propan-2-ol(Figure 11). 2-[2-(2-Amino-ethoxy)-ethoxy]-ethylamine (5.40 g; 36.4mMol) and 40 mL of ethanol were charged to a 100 ml RB flask equippedwith a magnetic stirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities and excess raw material.

-   Figure 11. Reaction Sequence for Preparation of Silane 11.

Preparation Example 12

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-morpholin-4-yl-propan-2-ol(Figure 12). Morpholine (0.634 g; 7.28 mMol) and 40 mL of ethanol werecharged to a 100 mL RB flask equipped with a magnetic stirrer. Themixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities.

-   Figure 12. Reaction Sequence for Preparation of Silane 12.

Preparation Example 13

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-piperazin-1-yl-propan-2-ol(Figure 13). Piperazine (3.14 g; 36.4 mMol) and 40 mL of ethanol werecharged to a 100 mL RB flask equipped with a magnetic stirrer. Themixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities. Excess piperazine was removed by sublimation.

-   Figure 13. Reaction Sequence for Preparation of Silane 13.

Preparation Example 14

1-[4-(2-Dimethylamino-ethyl)-piperazin-1-yl]-3-{3-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-propan-2-ol(Figure 14). Dimethyl-(2-piperazin-1-yl-ethyl)-amine (1.14 g; 7.28 mMol)and 40 mL of ethanol were charged to a 100 mL RB flask equipped with amagnetic stirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities.

-   Figure 14. Reaction Sequence for Preparation of Silane 14.

Preparation Example 15

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-(2-pyrrolidin-1-yl-ethylamino)-propan-2-ol(Figure 15). 2-Pyrrolidin-1-yl-ethylamine (4.16 g; 36.4 mMol) and 40 mLof ethanol were charged to a 100 mL RB flask equipped with a magneticstirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities and excess 2-pyrrolidin-1-yl-ethylamine.

-   Figure 15. Reaction Sequence for Preparation of Silane 15.

Preparation Example 16

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-(2-hydroxy-ethylamino)-propan-2-ol(Figure 16). 2-Amino-ethanol (2.22 g; 36.4 mMol) and 40 mL of ethanolwere charged to a 100 mL R^(B) flask equipped with a magnetic stirrer.The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities and excess 2-amino-ethanol.

-   Figure 16. Reaction Sequence for Preparation of Silane 16.

Preparation Example 17

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-(2-morpholin-4-yl-ethylamino)-propan-2-ol(Figure 17). 2-Morpholin-4-yl-ethylamine (4.74 g; 36.4 mMol) and 40 mLof ethanol were charged to a 100 mL RB flask equipped with a magneticstirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities and excess 2-morpholin-4-yl-ethylamine.

-   Figure 17. Reaction Sequence for Preparation of Silane 17.

Preparation Example 18

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-[(tetrahydro-furan-2-ylmethyl)-amino]-propan-2-ol(Figure 18). C-(Tetrahydro-furan-2-yl)-methylamine (3.68 g; 36.4 mMol)and 40 mL of ethanol were charged to a 100 mL RB flask equipped with amagnetic stirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities and excess C-(Tetrahydro-furan-2-yl)-methylamine.

-   Figure 18. Reaction Sequence for Preparation of Silane 18.

Preparation Example 19

1-Diethylamino-3-{3-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-propan-2-ol(Figure 19). Diethylamine (2.66 g, 36.4 mMol) and 40 mL of ethanol werecharged to a 100 mL RB flask equipped with a magnetic stirrer. Themixture was stirred and heated to 60° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 60° C. for an additional 8 hours. Ethanol and diethylamine were stripped off on the rotovap. The mixture was distilled undervacuum to remove impurities.

-   Figure 19. Reaction Sequence for Preparation of Silane 19.

Preparation Example 20

1-Amino-3-{3-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-propan-2-ol(Figure 20). Aqueous ammonium hydroxide (25%; 10 g, 150 mMol) and 40 mLof ethanol were charged to a 100 mL RB flask equipped with a magneticstirrer. The mixture was stirred and heated to 50° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 50° C. for an additional 8 hours. Ethanol and water werestripped off on the rotovap. The mixture was distilled under vacuum toremove impurities.

-   Figure 20. Reaction Sequence for Preparation of Silane 20.

Preparation Example 21

1-Dimethylamino-3-{3-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-propan-2-ol(Figure 21). Aqueous dimethylamine (25%; 10 g, dimethyl amine 55 mMol)and 40 mL of ethanol were charged to a 100 mL RB flask equipped with amagnetic stirrer. The mixture was stirred and heated to 50° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 50° C. for an additional 8 hours. Ethanol, water andexcess dimethyl amine were stripped off on the rotovap. The mixture wasdistilled under vacuum to remove impurities.

-   Figure 21. Reaction Sequence for Preparation of Silane 21.

Preparation Example 22

1-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-3-isopropylamino-propan-2-ol(Figure 22). Isopropylamine (2.15 g, 36.4 mMol) and 40 mL of ethanolwere charged to a 100 mL RB flask equipped with a magnetic stirrer. Themixture was stirred and heated to 60° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 60° C. for an additional 8 hours. Ethanol andisopropylamine were stripped off on the rotovap. The mixture wasdistilled under vacuum distillated to remove impurities.

-   Figure 22. Reaction Sequence for Preparation of Silane 22.

Preparation Example 23

1-Diisopropylamino-3-{3-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-propan-2-ol(Figure 23). Diisopropylamine (3.68 g, 36.4 mMol) and 40 mL of ethanolwere charged to a 100 mL RB flask equipped with a magnetic stirrer. Themixture was stirred and heated to 60° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 60° C. for an additional 8 hours. Ethanol anddiisopropylamine were stripped off on the rotovap. The mixture wasdistilled under vacuum to remove impurities.

-   Figure 23. Reaction Sequence for Preparation of Silane 23.

Preparation Example 24

6-[(3-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxy}-2-hydroxy-propyl)-methyl-amino]-hexane-1,2,3,4,5-pentaol(Figure 24). N-methyl-D-glucamine (1.42 g; 7.28 mMol) and 40 mL ofethanol were charged to a 100 mL RB flask equipped with a magneticstirrer. The mixture was stirred and heated to 70° C.2-{3-[Dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propoxymethyl}-oxirane8 (2 g; 7.28 mMol) mixed with 10 g ethanol was placed in an additionfunnel and added dropwise to the flask. The mixture was stirred andmaintained at 70° C. for an additional 4 hours. Ethanol was stripped offon the rotovap. The mixture was distilled under vacuum to removeimpurities.

-   Figure 24. Reaction Sequence for Preparation of Silane 24.

Comparative sample A is a trisiloxane ethoxylated surfactant containing8.5 polyoxyethylene repeat units. This product is commercially availableas Silwet® L-77 from GE Advanced Materials, Wilton, Conn.

Additionally, comparative sample OPE (Octylphenolethoxylate, containing10 polyoxyethylene units) is a non-silicone organic surfactant. Thisproduct is available as Triton® X-100 from Dow Chemical Company,Midland, Mich.

Example 1

This example demonstrates the ability of the silane compositions of thepresent invention to reduce aqueous surface tension, thereby showingutility as surfactants. Surface tension was measured using pendant dropanalysis. Solutions of the various components were prepared at 0.1 wt %in water (deionized), 2M NH₄Cl solution, or 10 wt. % NaCl solution.

Table 1 shows that solutions of these unique compositions provide asignificant reduction in surface tension relative to the conventionalsurfactant.

The compositions of the present invention also provide spreadingproperties similar to the comparative trisiloxane surfactant A.Additionally, silanes of the present invention provide improvedspreading relative to the conventional organic surfactant product OPE.

Spreading was determined by applying a 10 μL droplet, of surfactantsolution to polystyrene Petri dishes (Fisher Scientific) and measuringthe spread diameter (mm) after 30 seconds, at a relative humiditybetween 50 and 70% (at 22 to 25° C.). The solution was applied with anautomatic pipette to provide droplets of reproducible volume. Deionizedwater that was further purified with a Millipore filtration system wasused to prepare the surfactant solutions.

TABLE 1 Surface Tension and Spreading Properties Spread Diameter (mm)Surface 0.1 Weight % Surfactant Tension DI 2M 10% I.D. (mN/m) WaterNH₄Cl NaCl 2 31.4 5 nd 17 4 23.6 4 nd 40 5 45.0 4 nd 33 6 27.9 4 nd 10 727.4 4 nd nd 9 22.6 44 33 nd 10 22.0 45 42 nd 11 22.3 34 8 nd 12 23.5 740 nd 13 22.3 9 30 nd 14 23.1 29 18 nd 15 22.8 14 16 nd 16 22.6 14 35 nd17 22.2 36 36 nd 18 23.8 8 36 nd 19 22.9 4 40 nd 20 22.7 6 45 nd 21 21.96 50 nd 22 20.7 5 37 nd 23 Insol 4 50 nd 24 22.7 11 30 nd A 20.9 53 ndnd OPE 31.8 9 nd nd

Example 2

Unlike traditional siloxane based surfactants, which are subject torapid hydrolysis under acidic and basic conditions (≦pH 5 and ≧pH 9),the silanes of the present invention provide increased resistance tohydrolysis relative to traditional trisiloxane alkoxylates (ComparativeExample A). An artifact of hydrolysis is observed as a reduction inspreading properties over time. Therefore, solutions of the silanes ofthe present invention, as well as comparative surfactants, were preparedat desired use levels and pH. Spreading was determined as a function oftime to illustrate resistance to hydrolysis.

Table 2 is an illustrative example of a traditional organomodifiedtrisiloxane ethoxylate surfactant, which exhibits decreased spreadingperformance with time as a function of hydrolytic decomposition over apH range from pH 3 to pH 10. Here a 0.4 wt % solution of sample A wasprepared at pH 3, 4, 5 and 10. Spreading was determined by applying a 10μL droplet of surfactant solution to polyacetate film (USI, “CrystalClear Write on Film”) and measuring the spread diameter (mm) after 30seconds, at a relative humidity between 50 and 70% (at 22 to 25° C.).The solution was applied with an automatic pipette to provide dropletsof reproducible volume. Deionized water that was further purified with aMillipore filtration system was used to prepare the surfactantsolutions.

TABLE 2 Effect of pH on Spreading Properties Vs. Time Spread Diameter(mm) Time Product pH 3 pH 4 pH 5 pH 10 0 h A 34 28 29 27 1 h A 39 37 2733 2 h A 36 30 33 33 4 h A 41 28 28 29 6 h A 16 27 27 28 8 h A 12 31 2927 24 h A 12 32 25 25 48 h A 10 41 25 33 5 days A 7 30 26 36 7 days A 617 28 25 14 days A 7 7 37 15

Example 3

Table 3 is an illustrative example of an silane of the presentinvention, where sample 4, a superspreader, has improved resistance tohydrolysis, over a pH range from pH 4 to pH 11 relative to a traditionaltrisiloxane ethoxylate surfactant (Product A). As mentioned above,resistance to hydrolysis was observed by monitoring the spreadingproperties over time. Here a 0.1 wt % solution of surfactant wasprepared in distilled water containing 10 wt. % NaCl at pH 4, 5, 9 and11. Spreading was determined by applying a 10 μL droplet, of surfactantsolution to polystyrene Petri dishes (Fisher Scientific) and measuringthe spread diameter (mm) after 30 seconds, at a relative humiditybetween 50 and 70% (at 22 to 25° C.). The solution was applied with anautomatic pipette to provide droplets of reproducible volume.

TABLE 3 Effect of pH on Spreading Properties Vs. Time Spread Diameter(mm) Time Product pH 4 pH 5 pH 9 pH 11 0 h 4 43 44 43 44 24 h 4 43 44 4242 192 h 4 46 45 42 42 2 weeks 4 46 45 41 41 1 month 4 46 45 40 43 2months 4 45 46 42 41

Example 4

Table 4 is an illustrative example of an silane of the presentinvention, where sample 5, a superspreader, has improved resistance tohydrolysis, over a pH range from pH 4 to pH 11 relative to a traditionaltrisiloxane ethoxylate surfactant (Product A). As mentioned above,resistance to hydrolysis was observed by monitoring the spreadingproperties over time. Here a 0.1 wt % solution of surfactant wasprepared in distilled water containing 10 wt. % NaCl at pH 4, 5, 9 and11. Spreading was determined by applying a 10 μL droplet, of surfactantsolution to polystyrene Petri dishes (Fisher Scientific) and measuringthe spread diameter (mm) after 30 seconds, at a relative humiditybetween 50 and 70% (at 22 to 25° C.). The solution was applied with anautomatic pipette to provide droplets of reproducible volume.

TABLE 4 Effect of pH on Spreading Properties Vs. Time Spread Diameter(mm) Time Product pH 4 pH 5 pH 9 pH 11 0 h 5 18 18 20 21 24 h 5 19 18 2225 192 h 5 19 18 21 24 2 weeks 5 22 20 24 26 1 month 5 19 20 24 24 2months 5 22 23 24 26

The foregoing examples are merely illustrative of the invention, servingto illustrate only some of the features of the present invention. Theappended claims are intended to claim the invention as broadly as it hasbeen conceived and the examples herein presented are illustrative ofselected embodiments from a manifold of all possible embodiments.Accordingly it is the Applicants intention that the appended claims arenot to be limited by the choice of examples utilized to illustratefeatures of the present invention. As used in the claims, the word“comprises” and its grammatical variants logically also subtend andinclude phrases of varying and differing extent such as for example, butnot limited thereto, “onsisting essentially of” and “onsisting of.”Where necessary, ranges have been supplied, those ranges are inclusiveof all sub-ranges there between. Such ranges may be viewed as a Markushgroup or groups consisting of differing pairwise numerical limitationswhich group or groups is or are fully defined by its lower and upperbounds, increasing in a regular fashion numerically from lower bounds toupper bounds. It is to be expected that variations in these ranges willsuggest themselves to a practitioner having ordinary skill in the artand where not already dedicated to the public, those variations shouldwhere possible be construed to be covered by the appended claims. It isalso anticipated that advances in science and technology will makeequivalents and substitutions possible that are not now contemplated byreason of the imprecision of language and these variations should alsobe construed where possible to be covered by the appended claims. AllUnited States patents (and patent applications) referenced herein areherewith and hereby specifically incorporated by reference in theirentirety as though set forth in full.

1. A composition comprising a silane having the formula:(R¹)(R²)(R³)Si—R⁴—Si(R⁵)(R⁶)(R⁷) wherein R¹, R², R³, R⁵ and R⁶ are eachmethyl; R⁴ is a hydrocarbon group of 1 to 3 carbons; R⁷ is selected fromthe group consisting of R⁹—R^(C) and R¹⁰—R^(Z); R⁹ is a monovalentradical selected from the group consisting of R¹⁶(O)_(w)(R¹⁷)_(x)— andR¹⁸O(C₂H₄O)_(d)(C₃H₆O)_(e)(C₆H₈O)_(f)CH₂CH(OH)CH₂; where R¹⁶ and R¹⁷ areeach independently selected from the group consisting of a divalenthydrocarbon group of 1 to 4 carbon atoms; R¹⁸ is a divalent hydrocarbongroup of 2 to 4 carbon atoms; subscripts w and x are 1; the subscriptsd, e and f are zero or positive and satisfy the following relationships:1≦d+e+f≦10 with d≧1; R^(C) is selected from the group consisting ofN(R¹⁹)(R²⁰),

where R¹⁹ and R²⁰ are independently selected from the group consistingof H, a branched or linear monovalent hydrocarbon radical of 1 to 4carbons, R²⁶N(R²⁹)(R³⁰), and —R²⁷O(C₂H₄O)_(g)(C₃H₆O)_(h)(C₄H₈O)_(i)R²⁸;the subscripts g, h and i are zero or positive and satisfy the followingrelationships:1≦g+h+i≦10 with g≧1; R²¹, R²³, R²⁴, R²⁵ are each independently selectedfrom the group consisting of H and branched or linear monovalenthydrocarbon radicals of 1 to 4 carbons; R²² is a monovalent radicalselected from the group consisting of H, branched or linear monovalenthydrocarbon radical of 1 to 4 carbons, and—R³¹O(C₂H₄O)_(j)(C₃H₆O)_(k)(C₄H₈O)_(l)R³²; the subscripts j, k and 1 arezero or positive and satisfy the following relationships:1≦j +k+l≦10 with j≧1; R²⁶ is a divalent hydrocarbon radical of 1 to 6carbons, or R³³O(C₂H₄O)_(m)(C₃H₆O)_(n)(C₄H₈O)_(o)R³⁴; the subscripts m,n and o are zero or positive and satisfy the following relationships:1 ≦m+n+o≦10 with m≧1; R²⁹ and R³⁰ are independently selected from thegroup consisting of H, branched monovalent hydrocarbon radical of 1 to 4carbons, and linear monovalent hydrocarbon radical of 1 to 4 carbons;R²⁷, R³¹ and R³³ are independently selected from the group consisting ofa divalent hydrocarbon group of 2 to 4 carbon atoms; R²⁸ is a monovalentradical selected from the group consisting of H, a monovalenthydrocarbon radical of 1 to 6 carbons and N(R⁴⁰)(R⁴¹); R³² and R³⁴ areindependently selected from the group consisting of H, a branched orlinear monovalent hydrocarbon radical of 1 to 4 carbons, andR³⁷N(R³⁸)(R³⁹); where R³⁷ is a divalent hydrocarbon radical of 1 to 6carbons; R³⁵, R³⁶, R³⁸ and R³⁹ are independently selected from the groupconsisting of H and branched or linear monovalent hydrocarbon radicalsof 1 to 4 carbons; R¹⁰ is a monovalent radical selected from the groupconsisting of R⁴⁰(O)_(y)(R⁴¹)_(z)— andR⁴²O(C₂H₄O)_(p)(C₃H₆O)_(q)(C₆H₈O)_(r)CH₂CH(OH)CH₂—; where R⁴⁰ and R⁴¹are each independently selected from the group consisting of a divalenthydrocarbon group of 1 to 4 carbon atoms; R⁴² is a divalent hydrocarbongroup of 2 to 4 carbon atoms; the subscripts y and z are 1; thesubscripts p, q and r are zero or positive and satisfy the followingrelationships:1 ≦p+q+r≦10 with p≧1; R^(Z) is —N—(R⁴³)(R⁴⁴)_(α)R⁴⁵SO₃(M^(K))_(β),—N—(R⁴⁶)(R⁴⁷)_(γ)R⁴⁸COO(M^(K))_(δ), —N⁺—(R⁴⁹)(R⁵⁰)R⁵¹OP(═O)(A)(B) or,(—C(═O)N(R⁵²)R⁵³N—(R⁵⁴)(R⁵⁵))⁺—(R⁵⁶(═O)(A)(B)(X⁻)_(ε); where R⁴³, R⁴⁴,R⁴⁶, R⁴⁷, R⁴⁹, R⁵⁰, R⁵², R⁵⁴ and R⁵⁵ are independently selected from thegroup consisting of H, branched monovalent hydrocarbon radical of 1 to 4carbons, linear monovalent hydrocarbon radical of 1 to 4 carbons and analkanolamine group having alkyl groups of 2 to 4 carbons; and R⁴⁵ is adivalent group of 3 to 4 carbons; M^(K) is a cation selected from thegroup consisting of Na⁺, K⁺, Ca²⁺, NH⁴⁺, and Li⁺, monovalent ammoniumions derived from mono-, di- and trialkylamines comprising alkyl groupsof 2 to 4 carbons, and mono-, di- and trialkanolamines comprising alkylgroups of 2 to 4 carbons; subscripts α, β, γ and δ are zero or 1 subjectto the following relationships:α+β=1 and γ+δ=1; R⁴⁸ and R⁵¹ are independently a divalent group of 1 to4 carbons; R⁵³ and R⁵⁶ are each independently a divalent group of 2 to 4carbons; A and B are selected from O— and OM^(K); X is an anion selectedfrom the group consisting of CI, Br, and I; and the subscript ε is 0, 1or
 2. 2. The composition of claim 1 where R⁷ is R⁹- R^(C).
 3. Thecomposition of claim 1 where R^(C) is N(R¹⁹)(R²⁰).
 4. The composition ofclaim 1 where R⁷ is R¹⁰- R^(Z).
 5. The composition of claim 1 whereR^(Z) is —N—(R⁴³)(R⁴⁴)_(α)R⁴⁵SO₃(M^(K))_(β).
 6. The composition of claim1 where R^(Z) is —N—(R⁴⁶)(R⁴⁷)_(γ)R⁴⁸COO(M^(K))_(δ).